N-benzyl-m-phenylenediamine derivatives and dyes containing said compounds

Abstract

N-benzyl-m-phenylenediamine derivatives of general formula (I) or the physiologically tolerated, water-soluble salts thereof and dyeing agents for keratin fibers containing these compounds.

1. An N-Benzyl-m-phenylenediamine derivatives of general formula (I) or the physiologically-tolerated, water-soluble salts thereof, 
       
         
           
           
               
               
           
         
       
       wherein R1 denotes a halogen atom, a C 1 –C 4 -alkoxy group, a C 1 –C 4 -fluoroalkoxy group, a (C 1 –C 4 -alkyl)sulfamido-(C 2 –C 4 -alkoxy) group, a (C 1 –C 4 -alkyl)sulfonyl-(C 2 –C 4 -alkoxy) group, a C 2 –C 4 -hydroxyalkoxy group, a C 3 –C 4 -dihydroxyalkoxy group, a C 1 –C 6 -alkyl group, a C 1 –C 4 -alkylthioether group, a C 2 –C 4 -aminocarbonylalkoxy group, an aminoalkyl group, a trifluoromethyl group, an —Si(CH 3 ) 3  group, a C 1 –C 4 -hydroxyalkyl group or a C 3 –C 4 -dihydroxyalkyl group;
 R2 and R3 independently of each other denote hydrogen or a C 1 –C 4 -alkyl group, 
 R4, R5, R6, R7 and R8 independently of each other denote hydrogen , a halogen atom, a hydroxyl group, a (C 1 –C 4 )-alkoxy group, a hydroxy-(C 2 –C 4 )-alkoxy group, a (C 1 –C 6 )-alkyl group, a (C 1 –C 4 )-alkylthioether group, a mercapto group, an amino group, a (C 1 –C 6 )-alkylamino group, a di(C 1 –C 6 )-alkylamino group, a di[hydroxy-(C 2 –C 4 )-alkyl]amino group, a hydroxy-(C 2 –C 4 )-alkylamino group, a trifluoromethyl group, an acetamido group, a —C(O)Ch 3  group, a —C(O)Cf 3  group, an —Si(CH 3 ) 3  group, a hydroxy-(C 1 –C 4 )-alkyl group or a dihydroxy-(C 2 –C 4 )-alkyl group, or R5 and R6 together form an —O—CH 2 —O— bridge;
 with the proviso that R4 and R7 do not simultaneously each denote an amino group or that R5 and R8 do not simultaneously each denote an amino group; that R1 does not denote a CH 3  group when each of R2, R3, R4, R5, R8, R7 and R8 denotes hydrogen; that R1 does not denote a OCH 3  group when simultaneously R2 denotes an isopropyl group and each of R3, R4, R5, R6, R7 and R8 denote hydrogen; that R1 does not denote hydrogen when simultaneously R2 denotes an isopropyl group, R4 denotes bromine and each of R3, R5, R6, R7 and R8 denote hydrogen or R8 denotes bromine and each of R3, R4, R5, R6 and R7 denote hydrogen; and that R1 does not denote methyl when simultaneously R2 denotes an isopropyl group, R4 denotes bromine and each of R3, R5, R6, R7 and R8 denote hydrogen or RB denotes bromine and each of R3, R4, R5, R6 and R7 denote hydrogen. 
 
 
     
     
       2. An N-benzyl-m-phenylenediamine derivative, or a water-soluble salt thereof, wherein said N-benzyl-m-phenylenediamine derivative is selected from the group consisting of 4-amino-2-{[5-amino-2-(2-hydroxyethoxy)-phenylamino]methyl}-phenol, 4-amino-2-{[5-amino-4-(2-hydroxyethoxy)-phenylamino]methyl}-phenol, 2-[4-amino-2-(3,5-diamino-benzylamino)phenoxy]ethanol, 2-[4-amino-2-(4-dimethylamino-benzylamino)-phenoxy]-ethanol, 2-[4-amino-2-(4-methoxy-benzylamino)-phenoxy]-ethanol, 2-(4-amino-2-benzyl-aminophenoxy)-ethanol, 2-{4-amino-2-[(pyridin-2-ylmethyl)-amino]-phenoxy}-ethanol, 2-[4-amino-2-(2-methoxy-benzylamino)-phenoxy]-ethanol, 2-[4-amino-2-(2-amino-benzyl-amino)phenoxy]-ethanol, 3-[(4-{[5-amino-2-(2-hydroxy-ethoxy)-phenylamino]-methyl}-phenyl)-(2-cyanoethyl)-amino]-propionitrile, 2-[4-amino-2-(4-amino-benzylamino)-phenoxy]ethanol, 2-[(4-{[5-amino-2-(2-hydroxyethoxy)phenyl-amino]methyl}-phenyl)-(2-hydroxyethyl)amino]-ethanol, 2-{[5-amino-2-(2-hydroxyethoxy)-phenylamino]-methyl}-benzene-1,4-diol, 2-[4-amino-2-(4-nitrobenzylamino)-phenoxy]-ethanol, 2-[4-amino-2-(3-aminobenzylamino)-phenoxy]-ethanol, 2-(4-{[5-amino-2-(2-hydroxy-ethoxy)phenyl-amino]-methyl}-phenoxy)-ethanol, N-(4-{[5-amino-2-(2-hydroxyethoxy)-phenylamino]-methyl}-phenyl)-acetamide, 4-{[5-amino-2-(2-hydroxyethoxy)-phenylamino]methyl}-phenol, 3-{(5-amino-2-(2-hydroxyethoxy)-phenylamino]-methyl}-phenol, 2-{[5-amino-2-(2-hydroxy-ethoxy)-phenylamino]-methyl}-phenol, 4-{[5-amino-2-(2-hydroxyethoxy)-phenyl-amino]-methyl}-benzoic acid, 2-[4-amino-2-(2-morpholin-4-yl-benzylamino)-phenoxyethenol, 3-[4-amino-2-(3,5-diamino-benzylamino)phenoxy]-propanol, 3-[4-amino-2-(4-dimethylaminobenzylamino)-phenoxy]-propanol, 3-(4-amino-2-(4-methoxybenzylamino)-phenoxy]-propanol, 3-(4-amino-2-benzlamino-phenoxy)-propanol, 3-{4-amino-2-[(pyridin-2-ylmethyl)-amino]phenoxy}-propanol, 3-[4-amino-2-(2-methoxybenzylamino)phenoxy]-propanol, 3-[4-amino-2-(2-aminobenzylamino)phenoxy]-propanol, 3-[4-amino-2-(4-aminobenzyl-amino)-phenoxy]-propanol, 3-[(4-{[5-amino-2-(2-hydroxyethoxy)-phenylamino]-methyl}-phenyl)-(2-hydroxyethyl)amino]propanol, 3-[4-amino-2-(4-nitrobenzyl-amino)-phenoxy]-propanol, 3-[4-amino-2-(3-aminobenzylamino)-phenoxy]-propanol, 3-(4-{[5-amino-2-(2-hydroxyethoxy)phenylamino]-methyl}-phenoxy)-propanol, 4-{[5-amino-2-(3-hydroxypropoxy)phenylamino]-methyl}-phenol, 2-{[5-amino-2-(3-hydroxy-propoxy)phenylamino]-methyl}-phenol, 2-{[5-amino-2-(3-hydroxypropoxy)-phenylamino]-methyl}-phenol, 3-[4-amino-2-(2-morpholin-4-yl-benzylamino)-phenoxy]-propanol, N 3 -benzyl-1,3-diamino-4-(2-methoxy-ethoxy)-benzene, N 3 -(3-aminobenzyl)-1,3-diamino-4-(2-methoxy-ethoxy)-benzene, N 3 -(2-amino-benzyl)-1,3-diamino-4-(2-methoxyethoxy)-benzene, N 3 -(4-aminobenzyl)-1,3-diamino-4-(2-methoxyethoxy)-benzene, 3-{[5-amino-2-(2-methoxyethoxy)-phenylamino]methyl}-phenol, 2-{[5-amino-2-(2-methoxy-ethoxy)-phenylamino]-methyl}phenol, 4-{[5-amino-2-(2-methoxy-ethoxy)-phenyl-amino]-methyl}-phenol, N 3 -benzyl-1,3-diamino-4-methoxy-benzene, N 3 -(3-amino-benzyl)-1,3-diamino-4-methoxybenzene, N 3 -(2-aminobenzyl)-1,3-diamino-4-methoxybenzene, N 3 -(4-aminobenzyl)-1,3-diamino-4-methoxybenzene, 3-{[5-amino-2-methoxy-phenylamino]-methyl}-phenol, 2-{[5-amino-2-methoxy-phenylamino]-methyl}-phenol, 4-{[5-amino-2-methoxy-phenyl-amino]-methyl}-phenol, N 3 -benzyl-1,3-diamino-4-fluorobenzene, N 3 -(3-aminobenzyl)-1,3-diamino-4-fluorobenzene, N 3 -(2-aminobenzyl)-1,3-diamino-4-fluorobenzene, N 3 -(4-amino-benzyl)-1,3-diamino-4-fluorobenzene, 3-{[5-amino-2-fluoraphenylamino]-methyl}-phenol, 2-{[5-amino-2-fluorophenyl-amino]-methyl}-phenol, and 4-{[5-amino-2-fluoro-phenylamino]methyl}-phenol. 
     
     
       3. The N-benzyl-m-phenylenediamine derivative, or the water-soluble salt thereof, as defined in  claim 1 , wherein R2 and R3 each denote hydrogen; R1 denotes a C 2 –C 4 -hydroxyalkoxy group and R2 and R3 each denote hydrogen; or R1 denotes a C 2 –C 4 -hydroxyalkyl group, R2 and R3 each denote hydrogen and four of R4, R5, R6, R7 and R8 denote hydrogen while a remaining one of R4, R5, R6, R7 and R8 denotes hydrogen, a methoxy group, a hydroxy group, a methyl group or an amino group. 
     
     
       4. The N-benzyl-m-phenylenediamine derivative, or the water-soluble salt thereof, as defined in  claim 1 , wherein said N-benzyl-m-phenylenediamine derivative is selected from the group consisting of 2-(4-amino-2-benzylamino-phenoxy)ethanol, 2-[4-amino-2-(2-aminobenzylamino)phenoxy]-ethanol, 2-[4-amino-2-(4-aminobenzylamino)phenoxy]ethanol, 2-[4-amino-2-(3-amino-benzylamino)phenoxy]ethanol, 4-{[5-amino-2-(2-hydroxyethoxy)-phenylamino]-methyl}phenol, 3-{[5-amino-2-(2-hydroxyethoxy)-phenylamino]-methyl}phenol, and 2-{[5-amino-2-(2-hydroxyethoxy)phenylamino]-methyl}phenol. 
     
     
       5. A composition for oxidative dyeing of keratin fibers, said composition containing at least one coupler and at least one developer;
 wherein said at least one coupler comprises at least one N-benzyl-m-phenylenediamine derivative of formula (I), or a physiologically tolerated, water-soluble salt thereof, 
 
       
         
           
           
               
               
           
         
       
       wherein R1 denotes a halogen atom, a C 1 –C 4 -alkoxy group, a C 1 –C 4 -fluoroalkoxy group, a (C 1 –C 4 -alkyl)sulfamido-(C 2 –C 4 -alkoxy) group, a (C 1 –C 4 -alkyl)sulfonyl-(C 2 –C 4 -alkoxy) group, a C 2 –C 4 -hydroxyalkoxy group, a C 3 –C 4 -dihydroxyalkoxy group, a C 1 –C 6 -alkyl group, a C 1 –C 4 -alkylthioether group, a C 2 –C 4 -aminocarbonylalkoxy group, an aminoalkyl group, a trifluoromethyl group, an —Si(CH 3 ) 3  group, a C 1 –C 4 -hydroxyalkyl group or a C 3 –C 4 -dihydroxyalkyl group;
 R2 and R3 independently of each other denote hydrogen or a C 1 –C 4 -alkyl group, 
 R4, R5, R6, R7 and R8 independently of each other denote hydrogen , a halogen atom, a hydroxyl group, a (C 1 –C 4 )-alkoxy group, a hydroxy-(C 2 –C 4 )-alkoxy group, a (C 1 –C 6 )-alkyl group, a (C 1 –C 4 )-alkylthioether group, a mercapto group, an amino group, a (C 1 –C 6 )-alkylamino group, a di(C 1 –C 6 )-alkylamino group, a di[hydroxy-(C 2 –C 4 )-alkyl]amino group, a hydroxy-(C 2 –C 4 )-alkylamino group, a trifluoromethyl group, an acetamido group, a —C(O)Ch 3  group, a —C(O)CF 3  group, an —Si(CH 3 ) 3  group, a hydroxy-(C 1 –C 4 )-alkyl group or a dihydroxy-(C 2 –C 4 )-alkyl group, or R5 and R6 together form an —O—CH 2 —O— bridge;
 with the proviso that R4 and R7 do not simultaneously each denote an amino group or that R5 and R8 do not simultaneously each denote an amino group; that R1 does not denote a CH 3  group when each of R2, R3, R4, R5, R8, R7 and R8 denotes hydrogen; that R1 does not denote a OCH 3  group when simultaneously R2 denotes an isopropyl group and each of R3, R4, R5, R6, R7 and R8 denote hydrogen; that R1 does not denote hydrogen when simultaneously R2 denotes an isopropyl group, R4 denotes bromine and each of R3, R5, R6, R7 and R8 denote hydrogen or R8 denotes bromine and each of R3, R4, R5, R6 and R7 denote hydrogen. 
 
 
     
     
       6. The composition as defined in  claim 5 , containing from 0.005 to 20 percent by weight of said at least one N-benzyl-m-phenylenediamine derivative of formula (I), or said physiologically tolerated, water-soluble salt thereof. 
     
     
       7. The composition as defined in  claim 5 , wherein said at least one developer is selected from the group consisting of 1,4-diaminobenzene; 1,4-diamino-2-methylbenzene; 1,4-diamino-2,6-dimethylbenzene; 1,4-diamino-3,5-diethyl-benzene; 1,4-diamino-2,5-dimethylbenzene; 1,4-diamino-2,3-dimethylbenzene; 2-chloro-1,4-diaminobenzene; 1,4-diamino-2-(thiophen-2-yl)benzene; 1,4-diamino-2-(thiophen-3-yl)benzene; 1,4-diamino-2-(pyridin-3-yl)benzene; 2,5-diaminobiphenyl; 1,4-diamino-2-methoxymethylbenzene; 1,4-diamino-2-aminomethyl-benzene; 1,4-diamino-2-hydroxymethylbenzene; 1,4-diamino-2-(2-hydroxyethoxy)benzene; 2-[2-(acetylamino)ethoxy]-1,4-diaminobenzene; 4-phenylaminoaniline; 4-dimethylaminoaniline; 4-diethylaminoaniline; 4-dipropyl-aminoaniline; 4-[ethyl-(2-hydroxyethyl)amino]aniline; 4-[di(2-hydroxyethyl)amino]-aniline; 4-[di(2-hydroxy-ethyl)amino]-2-methylaniline; 4-[(2-methoxyethyl)amino]-aniline; 4-[(3-hydroxy-propyl)amino]aniline; 4-[(2,3-dihydroxypropyl)amino]-aniline; 1,4-diamino-2-(2-hydroxyethyl)benzene; 1,4-diamino-2-(1-hydroxyethyl)-benzene; 1,4-diamino-2-(1-methylethyl)benzene; 1,3-bis[(4-aminophenyl)-(2-hydroxyethyl)amino]-2-propanol; 1,4-bis[(4-aminophenyl)-amino]butane; 1,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane; 4-aminophenol; 4-amino-3-methylphenol; 4-amino-3-(hydroxymethyl)phenol; 4-amino-3-fluorophenol; 4-methyl-aminophenol; 4-amino-2-(aminomethyl)phenol; 4-amino-2-(hydroxymethyl)-phenol; 4-amino-2-fluorophenol; 4-amino-2-[(2-hydroxyethyl)-amino)methyl-phenol; 4-amino-2-methylphenol; 4-amino-2-(methoxymethyl)phenol; 4-amino-2-(2-hydroxyethyl)phenol; 5-aminosalicylic acid; 2,5-diaminopyridine; 2,4,5,6-tetraaminopyrimidine; 2,5,6-triamino-4-(1H)-pyrimidone; 4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole; 4,5-diamino-1-(1-methylethyl)-1H-pyrazole; 4,5-diamino-1-[(4-methylphenyl)methyl]-1H-pyrazole; 1-[(4-chlorophenyl)methyl]-4,5-diamino-1H-pyrazole; 4,5-diamino-1-methyl-1H-pyrazole; 2-aminophenol; 2-amino-6-methylphenol; 2-amino-5-methylphenol and 2,4-dihydroxyphenol. 
     
     
       8. The composition as defined in  claim 5 , containing from 0.005 to 20 percent by weight of each of said at least one developer and said at least one coupler. 
     
     
       9. The composition as defined in  claim 5 , further comprising at least one direct dye compound. 
     
     
       10. The composition as defined in  claim 5 , consisting of a hair colorant. 
     
     
       11. The composition as defined in  claim 5 , wherein said N-benzyl-m-phenylenediamine derivative is selected from the group consisting of 4-amino-2-{[5-amino-2-(2-hydroxyethoxy)-phenylamino]methyl}-phenol, 4-amino-2-{[5-amino-4-(2-hydroxyethoxy)-phenylamino]methyl}-phenol, 2-[4-amino-2-(3,5-diamino-benzylamino)phenoxy]ethanol, 2-[4-amino-2-(4-dimethylamino-benzylamino)-phenoxy]-ethanol, 2-[4-amino-2-(4-methoxy-benzylamino)-phenoxy]-ethanol, 2-(4-amino-2-benzyl-aminophenoxy)-ethanol, 2-{4-amino-2-[(pyridin-2-ylmethyl)-amino]-phenoxy}-ethanol, 2-[4-amino-2-(2-methoxy-benzylamino)-phenoxy]-ethanol, 2-[4-amino-2-(2-amino-benzyl-amino)phenoxy]-ethanol, 3-[(4-{[5-amino-2-(2-hydroxy-ethoxy)-phenylamino]-methyl}-phenyl)-(2-cyanoethyl)-amino]-propionitrile, 2-[4-amino-2-(4-amino-benzylamino)-phenoxy]ethanol, 2-[(4-{[5-amino-2-(2-hydroxyethoxy)phenyl-amino]methyl}-phenyl)-(2-hydroxyethyl)amino]-ethanol, 2-{[5-amino-2-(2-hydroxyethoxy)-phenylamino]-methyl}-benzene-1,4-diol, 2-[4-amino-2-(4-nitrobenzylamino)-phenoxy]-ethanol, 2-[4-amino-2-(3-aminobenzylamino)-phenoxy]-ethanol, 2-(4-{[5-amino-2-(2-hydroxy-ethoxy)phenyl-amino]-methyl}-phenoxy)-ethanol, N-(4-{[5-amino-2-(2-hydroxyethoxy)-phenylamino]-methyl}-phenyl)-acetamide, 4-{[5-amino-2-(2-hydroxyethoxy)-phenylamino]methyl}-phenol, 3-{(5-amino-2-(2-hydroxyethoxy)-phenylamino]-methyl}-phenol, 2-{[5-amino-2-(2-hydroxy-ethoxy)-phenylamino]-methyl}-phenol, 4-{[5-amino-2-(2-hydroxyethoxy)-phenyl-amino]-methyl}-benzoic acid, 2-[4-amino-2-(2-morpholin-4-yl-benzylamino)-phenoxyethenol, 3-[4-amino-2-(3,5-diamino-benzylamino)phenoxy]-propanol, 3-[4-amino-2-(4-dimethylaminobenzylamino)-phenoxy]-propanol, 3-(4-amino-2-(4-methoxybenzylamino)-phenoxy]-propanol, 3-(4-amino-2-benzlamino-phenoxy)-propanol, 3-{4-amino-2-[(pyridin-2-ylmethyl)-amino]phenoxy}-propanol, 3-[4-amino-2-(2-methoxybenzylamino)phenoxy]-propanol, 3-[4-amino-2-(2-amino-benzylamino)phenoxy]-propanol, 3-[4-amino-2-(4-aminobenzyl-amino)-phenoxy]-propanol, 3-[(4-{[5-amino-2-(2-hydroxyethoxy)-phenylamino]-methyl}-phenyl)-(2-hydroxyethyl)amino]propanol, 3-[4-amino-2-(4-nitrobenzyl-amino)-phenoxy]-propanol, 3-[4-amino-2-(3-aminobenzylamino)-phenoxy]-propanol, 3-(4-{[5-amino-2-(2-hydroxyethoxy)phenylamino]-methyl}-phenoxy)-propanol, 4-{[5-amino-2-(3-hydroxypropoxy)phenylamino]-methyl}-phenol, 2-{[5-amino-2-(3-hydroxy-propoxy)phenylamino]-methyl}-phenol, 2-{[5-amino-2-(3-hydroxypropoxy)-phenylamino]-methyl}-phenol, 3-[4-amino-2-(2-morpholin-4-yl-benzylamino)-phenoxy]-propanol, N 3 -benzyl-1,3-diamino-4-(2-methoxyethoxy)-benzene, N 3 -(3-aminobenzyl)-1,3-diamino-4-(2-methoxyethoxy)-benzene, N 3 -(2-aminobenzyl)-1,3-diamino-4-(2-methoxyethoxy)-benzene, N 3 -(4-amino-benzyl)-1,3-diamino-4-(2-methoxyethoxy)-benzene, 3-{[5-amino-2-(2-methoxy-ethoxy)-phenylamino]methyl}-phenol, 2-{[5-amino-2-(2-methoxyethoxy)-phenyl-amino]-methyl}phenol, 4-{[5-amino-2-(2-methoxy-ethoxy)-phenylamino]-methyl}-phenol, N 3 -benzyl-1,3-diamino-4-methoxybenzene, N 3 -(3-aminobenzyl-1,3-diamino-4-methoxybenzene, N 3 -(2-amino-benzyl)-1,3-diamino-4-methoxy-benzene, N 3 -(4-aminobenzyl)-1,3-diamino-4-methoxybenzene, 3-{[5-amino-2-methoxy-phenylamino]-methyl}-phenol, 2-{[5-amino-2-methoxy-phenylamino]-methyl}-phenol, 4-{[5-amino-2-methoxy-phenyl-amino]-methyl}-phenol, N 3 -benzyl-1,3-diamino-4-fluorobenzene, N 3 -(3-aminobenzyl)-1,3-diamino-4-fluorobenzene, N 3 -(2-aminobenzyl)-1,3-diamino-4-fluorobenzene, N 3 -(4-amino-benzyl)-1,3-diamino-4-fluorobenzene, 3-{[5-amino-2-fluoraphenylamino]-methyl}-phenol, 2-{[5-amino-2-fluorophenyl-amino]-methyl}-phenol, and 4-{[5-amino-2-fluorophenylamino]methyl}-phenol.